CN109071215A - The method for producing hydrogen-rich gas - Google Patents
The method for producing hydrogen-rich gas Download PDFInfo
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- CN109071215A CN109071215A CN201780023672.6A CN201780023672A CN109071215A CN 109071215 A CN109071215 A CN 109071215A CN 201780023672 A CN201780023672 A CN 201780023672A CN 109071215 A CN109071215 A CN 109071215A
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- 239000007789 gas Substances 0.000 title claims abstract description 150
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000001257 hydrogen Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 27
- 239000011149 active material Substances 0.000 claims abstract description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 48
- 230000015572 biosynthetic process Effects 0.000 claims description 32
- 238000003786 synthesis reaction Methods 0.000 claims description 30
- 230000008859 change Effects 0.000 claims description 14
- 239000012530 fluid Substances 0.000 claims description 12
- 238000004891 communication Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 10
- 238000004064 recycling Methods 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 230000009466 transformation Effects 0.000 description 6
- 239000002918 waste heat Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 241001122767 Theaceae Species 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- -1 sulphur compound Chemical class 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010037211 Psychomotor hyperactivity Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/14—Details of the flowsheet
- C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
This disclosure relates to method and relevant process equipment for producing hydrogen-rich gas, comprising the following steps: (a) provides reactor feed gas, and it includes with the CO and H of drying meter at least 25%, 40% or 70%2Combination, and steam, (b) material for guiding the reactor feed gas and there is catalytic activity in water gas shift reaction, generate product gas, it is characterized in that, during the first stage of high recirculation operation, the product gas of first amount is recycled, to be contacted together with the reactor feed gas with the catalytically-active materials, and during the second stage of low recirculation operation, there is no the product gas or is recycled lower than the product gas of the second amount of first amount, to be contacted together with the reactor feed gas with the catalytically-active materials, the associated benefits of this method are the changes that can be carried out according to technological standards appropriate between operation mode, so that applying optimal process conditions always, operating cost is reduced simultaneously, including steam consumption.
Description
The present invention relates to the methods by synthesis gas production hydrogen-rich gas.The method includes addition steam and recycled products
The combination step of gas, to control process gas reactivity, is especially being urged especially during starting and under reduced load
Agent be it is fresh and have high activity when.
In the production of hydrogen-rich gas, it is added in the synthesis gas comprising CO using steam as reactant, according to water-gas
Conversion reaction, with H2O is reacted to form H2And CO2.Side reaction (especially at elevated temperatures) is methanation.In order to limit
Methanation processed, can be with the steam of excessive addition, so that there is reactor feed gas high steam/carbon monoxide (S:CO) to compare
(being higher than 2).
At elevated temperatures, the degree of methanation increases.Therefore, if the Temperature Distribution of reactor is well controllled,
Then methanation can keep negligible and can reduce S:CO ratio, lead to lower steam addition and relevant operation
Cost reduces.
Especially for fresh catalytically-active materials, the activity of conversion reaction and methanation reaction may be very high,
Therefore restrain this method to be important.Therefore, in the initial stage operated using fresh catalytically-active materials, it may be preferred to have
The configuration for thering is steam to add and recycle, but compared with the technique added or recycled with steam, this Process configuration will
Need the catalyst of higher volume.
It according to the disclosure, proposes at least during a part of catalyst lifetime, is added using recycling and steam
Combination operate for sour water gas shift reaction or sugar water gas shift reaction (sour or sweet water gas
Shift reaction) reactor to restrain reactivity.When the active quilt of the material in conversion reaction with catalytic activity
When sufficiently reducing, it is possible to reduce or omit the restraint for passing through recycling.Which ensure that reactor is maintained at facing lower than methanation
Boundary's temperature, while avoiding the reactive excessive restraint in routine operation.Advantageously, recycling gas can be driven by injector
Dynamic, injector has steam as power gas, to avoid the increase of operating cost and capital investment.
Definition:
Hereinafter, term Water gas shift/WGS technique (or conversion process) should be used for wherein CO and H2O reacts to form H2
And CO2Chemical technology.
Hereinafter, the transformation of term acid, which should be used to could be used without curing, closes the catalytically-active materials (example of object inactivation
Such as cobalt/molybdenum sulphide on carrier) the Water gas shift/WGS technique that occurs in the presence of sulphur compound.
Hereinafter, term sweet tea conversion process should be used for using to the sensitive catalytically-active materials of sulphur inactivation (such as
Cu zn/aluminium on carrier) the Water gas shift/WGS technique that occurs in the absence of sulphur compound.
Hereinafter, term methanation process (or formation of methane) should be used for wherein CO or CO2And H2Reaction is formed
CH4And H2The chemical technology of O.
Hereinafter, term synthesis gas (synthesis gas or syngas) should be to contain CO and H2Gas,
Middle CO and H2Merging concentration be at least 15%.
Hereinafter, concentration is provided based on volume.
Hereinafter, if concentration is stated with %, unless expressly stated otherwise, otherwise this be should be understood as based on dry
Dry volume (mole) %.
Hereinafter, the modulus (module) of synthesis gas should be defined as M=(H2-CO2)/(CO+CO2), show CO and
H2Between molecular equilibrium and compensate CO2Presence.
Hereinafter, when referring to bed or reactor, unless otherwise indicated herein, otherwise this can be understood as equivalent.
Hereinafter, when referring to operation stage, such stage can be in one or more reactors or reactor beds
Middle implementation.
Broad aspect of the invention is related to a kind of method for producing hydrogen-rich gas, comprising the following steps:
(a) reactor feed gas is provided, it includes with the CO and H of drying meter at least 25%, 40% or 70%2Group
Conjunction and steam,
(b) material for guiding the reactor feed gas and there is catalytic activity in water gas shift reaction,
Product gas is generated,
It is characterized in that,
During the first stage of high recirculation operation, the product gas of the first amount is recycled, with it is described anti-
Device feed gas is answered to contact together with the catalytically-active materials, and
During the second stage of low recirculation operation, without the product gas or lower than the second amount of first amount
The product gas be recycled, to be contacted with the reactor feed gas with the catalytically-active materials,
The associated benefits of this method are can to carry out the change between operation mode according to technological standards appropriate, make
It obtains and applies optimal process conditions always, while reducing operating cost, including steam consumption.
In another embodiment, according to the temperature to the material in water gas shift reaction with catalytic activity
Assessment carries out the change between the first stage of the high recirculation operation and the second stage of the low recirculation operation,
Relevant benefit is, can be with when the temperature of the material in water gas shift reaction with catalytic activity is lower
Recycling is reduced or avoided.It can be in the reactor or close to one or more monitoring positions of reactor temperature.
In another embodiment, according to the temperature to the material in water gas shift reaction with catalytic activity
Indirect assessment (such as from the secondhand parameter of process data relevant to temperature) carries out the first of the high recirculation operation
Change between stage and the second stage of the low recirculation operation.
In another embodiment, according to the assessment formed to product gas, the of the high recirculation operation is carried out
Change between one stage and the second stage of the low recirculation operation, relevant benefit are the composition reflections of product gas
The amount of unreacted CO in actual process operation, especially process gas.
In another embodiment, the synthesis gas include with the CO of drying meter at least 20% and with drying meter at most
70% CO, relevant benefit are that this synthesis gas is industrially related to the conversion of Water gas shift/WGS technique.
In another embodiment, it is this gas that the synthesis gas, which includes at least sulphur of 200ppm, relevant benefit,
Expensive desulfurization is not undergone.
In another embodiment, the product gas of the amount is driven by the injector with steam as power gas
Dynamic, relevant benefit is that injector is a simple equipment, is invested low with operating cost.
Another aspect of the present disclosure is related to a kind of for producing the process equipment of hydrogen-rich gas, comprising:
Reactor with entrance and exit,
With reactor recirculation line,
The process equipment is configured as receiving by different pipelines:
It is the synthesis air-flow and steam stream in the pipeline of fluid communication with reactor inlet, wherein the reactor accommodates
There is the material of catalytic activity in water gas shift reaction,
The recirculation line further includes the injector with power gas entrance, intake-gas entrance and exhaust outlet,
Wherein power gas entrance and the steam stream are to be in fluid communication, and intake-gas entrance and the reactor outlet are fluid company
It is logical, and the entrance of exhaust outlet and reactor is to be in fluid communication, and wherein the process equipment includes passing through institute for controlling
The device of the gas flow of intake-gas entrance sucking is stated,
Relevant benefit is, this process equipment is suitable for the operation of configurable technique, at the same make the operation it is miscellaneous at
This (overhead cost) is minimized, i.e., (a.o.) is due to using the cheap injector with lower operational cost.By with independence
Injector is driven in the independent steam pipe line of synthesis gas pipeline, provides the flexibility of recirculation volume.
In another embodiment, process equipment further includes the steam control valve with entrance and exit, is configured
At make automatic steam control valve inlet and the steam stream to be in fluid communication, and automatic steam control valve outlet and the reactor inlet
To be in fluid communication, relevant benefit is, the steam valve control is directed to the quantity of steam of injector as power gas, thus
Control recirculation volume.
In many chemical technologies, hydrogen is crucial reactant.It may need the hydrogen of pure hydrogen form, such as
Ammonia produces or for the hydrotreating in oil plant, or may need hydrogen and carbon monoxide composition, such as synthesizing first
Alcohol or synthetic natural gas or charging for Fischer-Tropsch technique.The a part of hydrogen as synthesis gas, in depositing for water
It is provided under by the gasification of carbonaceous material or hydrocarbon.In general, the amount of the carbon monoxide in synthesis gas is higher than needed for subsequent technique
Amount.However, in the presence of catalyst appropriate, pass through reacting for carbon monoxide and water, well-known water gas shift reaction
For " transforming " into hydrogen by the carbon monoxide partial in gas or completely.Reaction product includes CO2, simply and easily from conjunction
It is separated at gas.The method that the disclosure would commonly be used for referred to as acid transformation, usually using urging comprising cobalt and molybdenum or tungsten
Agent, and it has the benefit operated at moderate temperatures, and does not need except desulfuration from synthesis gas, but as secondary anti-
It answers, also has at elevated temperatures from CO and H2Catalysis forms methane rather than the trend of hydrogen.However, according to the disclosure
Method water gas shift reaction temperature control can also be such as used for other water gas converting catalysts sweet tea transformation urge
Agent is related.
The composition of synthesis gas depends on many aspects, the design including gasifier.Some examples of composition in Higman,
C.and van der Burgt, M.Gasification, Elsevier Inc. is provided in 2008.In general, oxygen combustion gasifies
Synthesis gas in device includes the H of 25-50%2With the CO and CO of 15-75%2Combination, it is also possible to there are other compositions, such as
At most 10% CH4.If gasifier operates in an atmosphere, forming will be naturally with N2Based on, so that other concentration reduce greatly
About 5 times.In addition, synthesis gas can also be provided by other techniques, so that composition can be different from above-mentioned composition, but CO and H2Conjunction
And concentration will be above 25%.
As described above, the formation of methane is the side reaction of water gas shift reaction, especially in so-called acid transformation catalysis
In agent, because sour transformation catalyst usually operates under the steam of medium stoichiometric excess.Methanogenesis be it is undesirable, should
Technique is exothermic and has overactivity temperature, and minimizes methanogenesis using various methods.It is most common
Measure be excessive addition steam to reduce the reactivity towards methanogenesis, to reduce reactor outlet temperature, and therefore
It avoids sintering of catalyst and restrains methanation reaction.The technique is usually designed in more sluggish methanation condition (example
Such as high excessive steam, to avoid the outlet temperature excessively high when catalytically-active materials have most highly active) under operate, but this has
The shortcomings that needing increased catalyst volume and therefore bigger reactor.
In addition, the steam addition more than stoichiometry needed for reaction is extra cost during operation, it is therefore desirable for
Reduce excessive steam addition.
The another way for controlling the technique is that had dilution feeding flow using recirculation flow and therefore reduced temperature liter
Effect that is high and reducing the residence time.However, also it is known that, this results in the need for increased catalyst volume, therefore increases
Cost of investment is added.In addition, recycling is traditionally related to compressor, it is related to cost with high investment and operating cost.
Now according to the present invention, it has been determined that a method of effectively control side reaction.In the process, according to technique
Parameter (such as temperature, the processing volume of synthesis gas or catalyst activity of catalytically-active materials) dynamically configures the technique.
Causing to overheat the risk highest initial stage due to excessive catalyst activity, excessive steam is being added to
In the charging of reactor, combined with the recycling from the stage product.Since catalyst initially has high activity, reaction
Even if (in the case where the recycling of restraint) is enough.After operating a period of time, the activity of catalyst is reduced, and can be subtracted
Recycling is blocked less or even, since it is desired that less restraint.
In a preferred embodiment, for being to use the steam of addition as power to the device that recirculation flow pressurizes
The injector of gas, this avoids in addition using the significant operation of compressor and cost of investment.In this respect, the journey of recycling
Degree can be controlled by controlling the amount of the steam sent as the power gas of injector, for example, by bypassing injector
And steam is conducted directly to the pipeline of reactor inlet.
Brief description
Fig. 1-4 shows the reactor in the Water gas shift/WGS Process configuration according to the disclosure, has what be can be changed to follow again
The different types of injector of ring driving and the mode of control recycling and steam addition.
Fig. 5 shows the reactor in conventional water-gas conversion process configuration according to prior art.
The list of element in attached drawing:
Feed synthesis gas 102,202,302,402,502
Major ingredient stream 106,506
Charging by-pass 110,510 for adjusting
Combined feeding flow 114,214,314,414,514
Steam 120,220,320,420,520
Recirculation flow 128,228,328,428
Product stream 124,224,324,424,524
Recycle product stream 126,226,326,426
Steam power stream 122,222,322,422
Cooling product stream 130,230,330,430,530
Product stream 134,536 that is transformed and adjusting
Water-gas shift 150,250,350,450,550
Waste heat boiler 152,252,352,452,552
Injector 254,354,
Variable injecting device 154,454
Recirculation control valve 360
Steam control valve 264,364
Bypass control valve 162,262
Fig. 1 shows the reactor in the Water gas shift/WGS Process configuration according to the disclosure, wherein having by variable injecting
The recycling around reactor of device driving.Feed synthesis gas 102 is divided into major ingredient stream 106 first and optional is used to adjust
Feed by-pass 110.Major ingredient stream 106 heats in heat exchanger 128 before merging with recirculation flow 128.By combined charging
Stream 114 is directed to water-gas shift 150, then the cooled product stream 124 for example in waste heat boiler 152, and generates steaming
Vapour, but the heat discharged can be used for other purposes.Depending on the setting of variable injecting device 154, a certain amount of cooled product
Stream can carry out recycling 126 around reactor.If injector is configured for recycling, drawn again by injector 154
Recycle stream 126 uses steam 120 as kinetic current.It is desirable to keep that the molar flow between 106 and 120 is than constant, to ensure to become
Change constant conversion of the CO to H2 in unit.In practice, it 102 and therefore 106 is provided by desired machine utilization, is then passed through
Inner needle valve combination bypass control valve 162 in variable injecting device 154 adjusts accordingly steam addition 120.Then, recirculation flow
126 determine reactor outlet temperature 124.Recirculating mass is controlled by the interior needle in injector.Can according in the reactor or
The temperature that measures in the outlet stream for carrying out autoreactor controls recirculation volume.Remaining product stream forms product gas flow 130,
The second water-gas shift (not shown) can be directed to.Product gas flow 130 can optionally be cooled and be used for
The charging by-pass 110 of adjusting merges to form product stream 134 that is transformed and adjusting.
Product gas flow 130 is optional with the merging for charging by-pass 110 for adjusting, and be can be omitted, for example,
If necessary to high mode (i.e. relative to CO, H2Amount it is high) product gas, especially if generating pure hydrogen.
Being further processed for product gas is known to the skilled in the art, and can for example be related to further becoming
Change reaction and the purification of product gas.
Similarly, it is also well known to those expert in the art that optional protection reactor can be located at the upstream of the reactor,
And feeding temperature can be controlled by being quenched with water.Quenching will have the effect that reaction is restrained in a manner of being similar to steam
Fruit.
Another embodiment of the technique will be provided in two or more shift-converters with catalytic activity
Material and quench intermediate gas with water, while from the second shift-converter recycled product gas.
Fig. 2 shows another embodiment according to the disclosure, wherein the reaction with Water gas shift/WGS Process configuration
Device, wherein having the recycling around reactor driven by injector.The embodiment that the embodiment is equal to Fig. 1, but
It is using external valve 264 and traditional injector 254.In general, be according to the variable injecting device of Fig. 1 preferably as its
Adjusting than having increased flexibility in terms of (turndown ratio), but according to fig. 2 have individual injector and
The configuration of valve is the simpler configuration for controlling recycling.Feed synthesis gas 202 is merged with recirculation flow 228.It will close
And the guidance of feeding flow 214 to water-gas shift 250, the then cooled product stream 224 in such as waste heat boiler 252,
And steam is generated, but the heat discharged can be used for other purposes.The product stream 226 of a certain amount of cooling can be by using
Steam 222 is recycled as the injector 254 of kinetic current around reactor, to reduce reactor outlet temperature.It is expected that protecting
The molar ratio (flow-rate ratio between i.e. 206 and 220) for holding steam and CO is constant, to ensure in converter unit CO to the constant of H2
Conversion.In practice, 202 and 206 being provided by desired machine utilization therefore, then by leading to the steam of injector 254
Valve 264 in pipeline adjusts accordingly steam addition 220.Then, recirculation flow 226 determines reactor outlet temperature 224.It follows again
Circulation is controlled by valve 262, which makes steam around injector 254.It can be according in the reactor or carrying out autoreactor
Outlet stream in the temperature that measures control recirculation volume.Remaining product stream forms product gas flow 230, can be directed to
Second water-gas shift (not shown).
Fig. 3 shows another embodiment according to the disclosure, wherein the reaction with Water gas shift/WGS Process configuration
Device, wherein having the recycling around reactor driven by injector.Here recirculation volume is by the valve in recirculation line
Control has flexibility more higher than the configuration that the steam in Fig. 1 and Fig. 2 bypasses injector, because can be independently adjusted
Steam addition and recirculating mass.Feed synthesis gas 302 is merged with recirculation flow 328.Extremely by the combined guidance of feeding flow 314
Water-gas shift 350, the then cooled product stream 324 in such as waste heat boiler 352, and steam is generated, but discharge
Heat can be used for other purposes.The product stream of a certain amount of cooling can spray by using steam 322 as kinetic current
Emitter 354 carries out recycling 326 around reactor.The ratio of total steam and CO is controlled by valve 364, and reactor outlet temperature is logical
Cross recirculation volume (that is, by regulating valve 360) control.It can be according to surveying in the reactor or in the outlet stream for carrying out autoreactor
The temperature of amount controls recirculation volume.Remaining product stream forms product gas flow 330, can be directed to the change of the second water-gas
Change reactor (not shown).
Fig. 4 shows another embodiment according to the disclosure, wherein the reaction with Water gas shift/WGS Process configuration
Device, wherein having the recycling around reactor driven by injector.Feed synthesis gas 402 is merged with recirculation flow 428.
By the combined guidance of feeding flow 414 to water-gas shift 450, the then cooled product stream in such as waste heat boiler 452
424, and steam is generated, but the heat discharged can be used for other purposes.
The product stream 426 of a certain amount of cooling can use steam 420 as kinetic current by what is controlled by inner needle valve
Variable injecting device 454 is recycled around reactor, and injector recycle efficiency is by adjusting the internal valve of injector 454 to produce
Recirculation flow 428 is given birth to limit.Recirculation volume is controlled by valve 460 according to desired technological temperature, and variable injecting device 454
Needle-valve will limit from 420 extract steam amount.It can be according to surveying in the reactor or in the outlet stream for carrying out autoreactor
The temperature of amount controls recirculation volume.Remaining product stream forms product gas flow 430, can be directed to the change of the second water-gas
Change reactor (not shown).
Fig. 5 shows the reactor in the process layout of Water gas shift/WGS according to prior art.Feed synthesis gas 502 is appointed
Selection of land is divided into major ingredient stream 506 and charging by-pass 510.Major ingredient stream 506 can optionally before it merges with steam stream 520
It is heated in heat exchanger.Combined feeding flow 514 is guided to water-gas shift 550, it is then cold in waste heat boiler 552
But intermediate product stream 524, and generate steam.The intermediate product stream of the cooling can be guided to the second water-gas shift
(not shown).Product gas flow 530 can also cool down in heat exchanger, and optionally with the charging by-pass 510 for adjusting
Merge, to form product stream 536 that is final transformed and adjusting.
Embodiment
In table 1, feed synthesis gas is characterized, corresponding to from the single-stage dryer feed gas operated under 1500 DEG C and 30 bars
Change the synthesis gas of device.It is assumed that feed flow rate is 200.000Nm3/h。
Table 1:
Seven embodiments of the Water gas shift/WGS technique of the feed synthesis gas of table 1 are had evaluated.All embodiments are equal
Based on feeding flow described in table 1, and need to produce the product gas (such as in order to produce synthesis gas) with modulus 3,
Suitable for producing synthetic natural gas, but similar principle is suitable for other desired product gas compositions.In some embodiments
In consider the entry condition of rated flow (nominal flow) and complete catalytic activity corresponding to 50%.In table 2, always
The operating characteristic of seven embodiments is tied.
Embodiment 1 (according to the prior art) corresponds to (end of run) catalyst of inactivation.It needs in this embodiment
77m3Catalytically-active materials, and resulting outlet temperature be 470 DEG C.Steam consumption is 155 ton/hours.
Embodiment 2 (according to the prior art) corresponds to entry condition as described above, the end of run based on embodiment 1
It is required that and designing.Resulting outlet temperature is 500 DEG C, is higher than desired range.
Embodiment 3 (according to the prior art) corresponds to the entry condition in such as embodiment 2, but passes through steam and add progress temperature
Degree is restrained, so that temperature becomes 470 DEG C.Compared with Example 2, additional 14t/h steam is needed during halfload starting, and
And in full load operation, this will become 28t/h.During catalyst life, the amount of excess steam can be reduced continuously.
Embodiment 4 considers the entry condition of an embodiment according to the disclosure, and display recycling and steam add
The combination added is provided to keep it is expected mould in product gas 470 DEG C (adding temperature obtained lower than with individual steam)
A possibility that number.In addition, compared with Example 3, steam additive amount reduces 30%.Be fed to the steam of reactor 51% is made
It is directed to injector for kinetic current, the recycling corresponding to 21% transformation product.
Embodiment 5, which is shown, increases to effect at full capacity from 50% load for production.In this example, space velocity drops
Low therefore required recirculation volume is slightly reduced.Compared with Example 1, steam addition reduces 20%.
Embodiment 6 and 7 is related to the catalyst of activity reduction, and they show, even if catalyst activity reduces at any time,
The combination of steam addition and recycling is also beneficial.By combining two kinds of Active Regulation factors, the quantity of steam of addition will be
127t/h, in contrast, being 155t/h in embodiment 1.
Embodiment show by implement recycling can to avoid steam is excessively added during starting, and further,
Implementing recycling will also reduce operating cost by the quantity of steam needed for reducing.The catalyst of higher volume may be needed, but
Reduced steam cost has been more than the increase of catalyst cost, especially if recycling is driven by injector, without operating
Cost simultaneously has the smallest cost of investment.
Table 2
Claims (9)
1. a kind of method for producing hydrogen-rich gas, comprising the following steps:
(a) reactor feed gas is provided, it includes with the CO and H of drying meter at least 40%, 70% or 85%2Combination, and
Steam,
(b) reactor feed gas is guided, with the material of catalytic activity, to generate in water gas shift reaction
Product gas,
It is characterized in that,
During the first stage of high recirculation operation, the product gas of the first amount is recycled, with the reactor
Feed gas is contacted with the catalytically-active materials together, and
During the second stage of low recirculation operation, without the product gas or lower than the product gas of first amount
The product gas of second amount of body is recycled, with together with the reactor feed gas with the catalytically-active materials
Contact.
2. according to the method described in claim 1, wherein according to the material in water gas shift reaction with catalytic activity
Temperature assessment, carry out between the first stage of the high recirculation operation and the second stage of the low recirculation operation
Change.
3. according to the method described in claim 2, wherein according to the material in water gas shift reaction with catalytic activity
Temperature indirect assessment assessment, carry out the high recirculation operation first stage and the low recirculation operation second
Change between stage.
4. method according to claim 1,2 or 3, wherein carrying out the height again according to the assessment to product gas composition
Change between the first stage of circulate operation and the second stage of the low recirculation operation.
5. method according to claim 1,2,3 or 4, wherein the synthesis gas is comprising with drying meter at least 20% and preferably
At most 70% CO.
6. according to claim 1, method described in 2,3,4 or 5, wherein the synthesis gas includes at least sulphur of 200ppm.
7. according to claim 1, method described in 2,3,4,5 or 6, wherein the product gas of the amount is dynamic by being used as with steam
The injector of strength body drives.
8. a kind of for producing the process equipment of hydrogen-rich gas, comprising:
Reactor with entrance and exit,
With reactor recirculation line,
The process equipment is configured as receiving by different pipelines:
It is the synthesis air-flow and steam stream in the pipeline of fluid communication with reactor inlet,
Wherein the reactor is contained in the material in water gas shift reaction with catalytic activity,
The recirculation line further includes the injector with power gas entrance, intake-gas entrance and exhaust outlet, wherein
Power gas entrance and the steam stream are fluid communication, intake-gas entrance and the reactor outlet to be in fluid communication, and
The entrance of exhaust outlet and reactor is to be in fluid communication, and wherein the process equipment includes passing through the suction for controlling
The device of the gas flow of gas access sucking.
9. process equipment according to claim 8 further includes the steam control valve with entrance and exit, is configured
At make automatic steam control valve inlet and the steam stream to be in fluid communication, and automatic steam control valve outlet and the reactor inlet
To be in fluid communication.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DKPA201600239 | 2016-04-25 | ||
| DKPA201600239 | 2016-04-25 | ||
| PCT/EP2017/059098 WO2017186526A1 (en) | 2016-04-25 | 2017-04-18 | Method for production of a hydrogen rich gas |
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| CN109071215A true CN109071215A (en) | 2018-12-21 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102695669A (en) * | 2009-11-05 | 2012-09-26 | 约翰森·马瑟公开有限公司 | Water gas shift reaction process |
| CN103897747A (en) * | 2013-11-25 | 2014-07-02 | 西门子公司 | Processing water gas from gasification device |
| CN203768005U (en) * | 2014-03-24 | 2014-08-13 | 中石化宁波工程有限公司 | Overtemperature circulation preventing CO conversion device |
| CN203768006U (en) * | 2014-03-24 | 2014-08-13 | 中石化宁波工程有限公司 | Energy-saving type circulating CO change device |
| WO2015062986A1 (en) * | 2013-10-28 | 2015-05-07 | Haldor Topsøe A/S | Process and reactor for exothermal reaction |
-
2017
- 2017-04-18 WO PCT/EP2017/059098 patent/WO2017186526A1/en active Application Filing
- 2017-04-18 CN CN201780023672.6A patent/CN109071215A/en active Pending
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2018
- 2018-09-04 ZA ZA2018/05928A patent/ZA201805928B/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102695669A (en) * | 2009-11-05 | 2012-09-26 | 约翰森·马瑟公开有限公司 | Water gas shift reaction process |
| WO2015062986A1 (en) * | 2013-10-28 | 2015-05-07 | Haldor Topsøe A/S | Process and reactor for exothermal reaction |
| CN103897747A (en) * | 2013-11-25 | 2014-07-02 | 西门子公司 | Processing water gas from gasification device |
| CN203768005U (en) * | 2014-03-24 | 2014-08-13 | 中石化宁波工程有限公司 | Overtemperature circulation preventing CO conversion device |
| CN203768006U (en) * | 2014-03-24 | 2014-08-13 | 中石化宁波工程有限公司 | Energy-saving type circulating CO change device |
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| Publication number | Publication date |
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| ZA201805928B (en) | 2024-01-31 |
| WO2017186526A1 (en) | 2017-11-02 |
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